Production of diazo prints



Patented Mar. 14, 19 39 I I t I I "UNITED, STATES: PATEN OFFICE emolluc'rlolz jz' r liazomm'rs. v

Paul Schmidt and 08hr Siis, Wiesbaden-Biebrich, Germany, aesignors to Kalle 8t 00. Aktiengesellschatt, Wiesbaden-Biebrlch,

Germany No Drawing. Application March 23, 1937, Serial No. 132,544. In Germany March 24, 1936 20 Claims. (01. 95-6) The present invention relates to the production sence of the alkyl group, the coupling with the of diazo prints and more particularly to a method diazo compound would take place, 1., e2: substances for the production of such prints, which is charwhich have the alkyl group in orthoor paraacterizedby the employment of certain azo composition to the hydroxy group, or to one of the 5 ponents possessing advantageous properties. One hydroxy groups as the case may be; Then, dur- 5 Object of the invention are therefore new azo ingthedevelopment thecoupling generally takes components for diazotype purposes; vAnother-ob- Place w th he split ing-oi! o! the substituted alky ject of the invention are light sensitive layers mum at the Position of the molecule 01 the 910 containing the said azo components. A further component at which the substituted alkyl group 10 object are developers particularly liquid developwas located the am components employed accordo ers which contain the said azo components. in to he inv n i n m y also e substituted by Hitherto only comparatively few serviceable further e ts 0 p 811011 88 alkyl G p compounds were available as azo components for chlorine, carboxyl B P and the like- Inasdiazotype purposes. The compounds must be much as it is intended that the 9.20 components s stable, last to light and-insensitive to alkali. It without e ubs itute allwl s ps should is is also important that they should be readily soluy soluble in water to the smallest possible exble in water, while, on the other hand, the dye-t tent. 1t is preferable that y Should not have stufls produced by the use of theme components slllpho ps On the hllclells- 311th should be as insoluble as possible. .The necessary stituents as di n the Stability of the M solubility in water has frequently been obtained Pollents Should 8,180 not he existentby the introduction of the. sulphonic acid group T upling energy of the new m' mll into the sac component. --'Ihe employment of 15, in general. ry Sm ll. whi h 13 0! gr a dsulphonic acids of this kind has, how t vantage for the production or two-component disadvantage that the dyestufis formed on cou- Papers capable of remaining stable h storedpling and consequently also the diazo prints are For this reason the new azo components can also 25 not very fast-to water. be employed with particular advantage for the Now, it has been discovered that as can couproduction of p o phic p i pape pling components substances can be employed adapted to be v p d with water or steam, which contain an aromatic nucleus carryingahyinasmuch as a small coupling energy with droxy group and a methyl group which latter layers which, in addition to the diazo and the azo 3 ries a substituent increasing the water-solubility, component! 6 the alkali 00 7 particularly a, basic t1t t The expression the development in the layer, nat y of parsolubility in water" is intended to include also miller importance the solubility in acidified water, i. e.,- the solubility Examples of some Preferred methods of munder the formation of salts. Compounds of mg h mvehtmn Practice are set forth I this kindar obtained, for xam le,b ondensin 10w:

e e p ye g (1) Asolution of 1.8 gramsoi the zinc chloride double salt of the diazo compound irom l-amino- 4-benzoylamino-2.5-diethoxy benzene. 1.8 cc. of

.aromatic or heterocyclic hydroxy compounds which are'capable of coupling with diazo com-, pounds, prei'erably'benzene or naphthalene compounds in known manner with aldehydes in the presence of organic secondary bases '(see, for example, German'Patent 89,979). Preferably one starts in this case from hydroxy compounds acid, 4 grams of tartaric acid, .21 gram oithiourea and 1.2 grams of I-methyI-o-dhnethyIamino-Z- hydroxy naphthalene I concentrated hydrochloric acid, 2 grams of boric which are insoluble or only dlmoulti oiuhle in I fi a. water. Azo components are obtained in this way cm-N 5 which iorm sufllciently easily soluble salts and in r spite oi that .yield prints possessing good fastness OH to water. The azo components may, if desired, also contain more than one alkyl' group substituted in the manner described, for example two groups of this kind. Several hydroxy groups may likewise be present. in '12 cc. 0! water is applied to paper. The de- According to the invention it is preferable to velopment oi'the paper can be eflected by means employ such substances ascarry the substituted of ammonia gas or an alkali solution, for example alkyl group at the position at which, in the .aba 4% solution of soda. I g5 Instead of the above-mentioned azo components 4-methyl-w piperidyl-l-hydroxy naphthalene can also be employed. This substance is produced by the condensation of l-naphthylcarbonic acid ethyl ester with formaldehyde hydrochloric acid to the chlormethyl compound and interchange of the chlorine with the piperidyl residue with simultaneous splitting ofi of the carbonic acid ethyl ester residue.

(2) 2 grams of the tin tetrachloride double salt of the diazo compound from l-amino-l- (N-benzyl-N-ethylamino)-benzene, .6 cc. of concentrated hydrochloric acid, .66 gram of boric acid, 1.5 grams of tartaric acid, .07 gram of thiourea and .5 gram of the hydrochloride of a con densation product which is obtained from equimolecular quantities of 2.6-dimethyl-8-hydroxy naphthalene and formaldehyde-dimethylamine, are dissolved in 50 cc. of water. The solution is applied in the usual manner to paper. The prints obtained therewith exhibit, on development with ammonia, a brown-black tone. Instead of the aforementioned azo component the condensation products from L-chlornaphthol or 1.8-chlornaphthol respectively with equimolecular quantities of formaldehyde and dimethylamine may be employed.

(3) A solution of 1.2 grams of the sulphate of the diazo compound from aminodiphenylamine, 1.2 cc. of concentrated hydrochloric acid, 1.32 grams of boric acid, 3 grams of tartaric acid, .2 gram of thiourea and 1 gram of the hydrochloride of a condensation product, which is obtained from equimolecular quantities of 3.5-dihydroxy-. benzoic acid and formaldehyde-dimethylamine in 72 cc. of water is applied to paper.

The red-browntone obtained with this paper on development of the prints undergoes an alteration in shade towards yellow-brown if, instead of the 3.5-dihydroxy-benzoic acid the 2.4-dihydroxy-benzoic acid is employed in the produc tion of the azo component.

(4) 3 grams of the zinc chloride double salt of the diazo compound from l-amino--benzoylamino-2.5-diethoxy-benzene, .4 gram of boric acid and 2 grams of the hydrochloride of a condensation product which is obtained from equimolecular quantities of 2.3-hydroxy-naphthoic acid and formaldehyde-dimethylamine, are dissolved in 100 cc. of water. Paper is coated with this solution. With the paper thus prepared prints are obtained which, in the first place, exhibit a brown tone, which after a little time passes over into deep blue-violet.

Instead of the above-named azo component the hydrochloride of a condensation product which is obtained from equimolecular quantities of. 3-hydroxydiphenylene oxide and formaldehyde-dimethylamine can be employed, or the compound from condensation product .of Z-hydroxy carbazole with formaldehyde and dimethylamine may also be employed.

(5) Paper is coated with a solution of 3 grams of the zinc chloride double salt of the diazo 1-amino-4-benzoylamino-2.5 diethoxy benzene, 1 gram of citric acid and 1 gram of aluminium sulphate in 100 cc. of water. The prints produced by means of a paper prepared in this manner are developed with a' solution containing 2 grams of sodium acetate and grams of the hydrochloride of a condensation product which is obtained from 1 molecule of 1.5- dihydroxy naphthalene and 2 molecules of formaldehyde-dimethylamine.

(6) A paper is coated with the sensitizing solution set forth in Example 5. The sensitized layer is rubbed over with an intimate mixture of equal parts of zinc acetate and of the azo component mentionedin Example 5. After exposure and subsequent development with steam, prints having deep blue tones are obtained.

(7) Paper is prepared by treatment with a solution of 3 grams of the, zinc chloride double salt of the diazo compound from 1-amino-4 benzoylamino-2.5-diethoxy benzene and .5 gram of tar taric acid in 100 cc. of Water. The development of the exposed paper is carried out by the use of a 5% aqueous solution of the sodium salt of l-methyl-w-(methyl methylcarboxy amino) -2- naphthol.

CHrCOONa GER-N The last-named compound is prepared by the condensation of equimolecular quantities of fi-naphthol, formaldehyde and N-methylaminoacetic acid.

(8) The procedure is as in Example '7. Instead of the azo component therein specified, however, the condensation product of B-naphthol with equimolecular quantities .of formaldehyde and N-methylaminoethane sulphonic acid is employed. I

(9) -1 gram of the diazo compound from p-aminodiethylaniline together with 1 gram of tartaric acid and 1.5,grams of the hydrochloride of the condensation product from 1 molecule of lA-dimethyl-Z-oxybenzene with equimolecular' quantities of formaldehyde and dimethylamine are dissolved in 50 cc. of water. By coating paper with this solution photographic printing material is obtained.

(10) 1 gram of the diazo compound mentioned dimethylamine.

3. Light sensitive diazotype material comprising a diazo compound and the condensation product obtained from equimolecular quantities of L-dimethyl-Z-oxyben'zene and formaldehydedimethylamine.

4. Developer for light sensitive diazotype material comprising an alkaline substance and 1- methyl-b-dimethybamino- 2 -hydroxy-naphthalene.

5. Developer for light sensitive diazotype material comprising an alkaline substance and the condensation product obtained from equimolecular quantities of 3.5-dihydroxy-benzoic acid and .formaldehyde-dimethylamine.

terial comprising an alkaline substance and the condensation product obtained from equimolecular quantities or 1.4-dimethyl-2-oxybcnzene and ty. 8. Light-sensitive diazotype material compris ing a diazo compound and a coupling component,

' which contains an aromatic nucleus carrying a hydroxy group and a methyl group, which latter carries a substituent increasing the water-solubility, the substituted methyl group being located in the molecule in the position in which the coupling takes place with accompanying scission of the substituted methyl group from the nucleus.

-9. Light-sensitive diazotype material comprising a diazo compound and a coupling component, which contains an aromatic nucleus carrying a hydroxy group and a methyl group, which latter carries a substituent increasing the water-solubility, the substituted methyl group being located in the molecule in the ortho-position to the hydroxy group.

10. Light-sensitive diazotype material comprising a diazo compound and a coupling component, which contains an aromatic nucleus carrying a hydroxy group and a methylgroup, which latter carries a substituent increasing the water-solubility, the substituted methyl group being located in the molecule in the droxy group. v 11. Light-sensitive diazotype material comprispara-position to the hying a diazo compound and a coupling component,

which contains an aromatic nucleus carrying a hydroxy group and a methyl group, which latter carries a basic substituent. 12. Light-sensitive diazotype material comprising a diazo compound. and a coupling component, which contains an aromatic nucleus carrying a hydroxy group and a dimethyl-amino-methyl group, the said dimethyl-amino-methyl group being located in the molecule in the position in which the coupling takes place with accompanying scission of the dimethyl-amino-methyl group from the nucleus.

13. Developer for light-sensitive diazotype maanalkaline substance and a coupling component, which contains an aromatic group, which. latter ing the water-solubility.

, terial comprising an 14. Developer for light-sensitive diazotype material comprising an alkalne substance and a coupling component, which contains an aromatic nucleus carrying a hydroxy group and a methyl group, which latter carries a substituent increasing the water-solub' ty, the substituted methyl group being located in the molecule in the position in which the coupling takes place with accompanying scission of the substituted methyl group from the nucleus.

15. Developer for light-sensitive diazotype ma-r terial comprising an alkaline substance and a coupling component, which contains an aromatic nucleus carrying a hydroxy group and a methyl group, which latter carries a substituent increasing the water-solubility, the substituted methyl group being located in the molecule in the orthoposition to the hydroxy group.

16. Developer for light-sensitive diazotype material comprising an alkaline substance and a coupling component, which contains an aromatic nucleus carrying a hydroxy group and a methyl group, which latter carries a substituent increasing the water-solubility, the substituted methyl group being located in the molecule in the paraposition to the hydroxy group.

17. Deyeloper for light-sensitive diazotype material comprising an alkaline substance and a coupling component, which contains an aromatic nucleus carrying a hydroxy groupand a. methyl group, which latter carries a basic substituent.

18. Developer for light-sensitive diazotype maalkaline substance and a coupling component, which contains a hydroxy group and a 'dimethyl-amino-methylgroup, the said dimethyl-amino-methyl group being located in the molecule in the position in which the coupling takes place with accompanying scission of the dimethyl-amino-methyl group from the nucleus.

19. Light-sensitive diazotype material comprising a diazo compound and a coupling component, which contains an aromatic nucleus carrying a hydroxy group and a methyl group, which latter carries an amino group as substituent.

20. Developer for light-sensitive diazotype material comprising an alkaline substance and a coupling component, which contains an aromatic nucleus carrying a hydroxy group and a methyl group, which latter carries an amino group as substituent.

PAUL scmrm'r.

OSKAR siis. 

